1. Field of the Invention
The present invention relates to cyclic amine based polymers which are substantially free of primary and secondary amino groups and a process for their production.
2. Background of the Invention
EP-B-0,209,787 relates to a process for the after-treatment of dyeings with reactive dyes on cellulose fiber materials with an aqueous solution of condensates which are obtained by first reacting piperazine, bis-1,4-aminopropylpiperazine, 1-aminoethylpiperazine, 2-hydroxyethylpiperazine or 1-methylpiperazine or mixtures thereof with a crosslinking agent selected from ethylene chloride, epihalohydrin, propylene chloride, 1,3-dichloro-2-hydroxypropane, bisepoxybutane, 1,4-dichlorobutane or a mixture thereof, in a molar ratio of from 1:0.5 to 1:1.1 and then benzylating the condensation products to such an extent that 15 to 90% of the tertiary nitrogen atoms in the condensation products are quaternized.
The use of polycationic condensates as color transfer inhibiting and color release reducing additive to detergents and to fabric conditioners is known from WO-A-98/17762. These water-soluble polycationic condensates are obtained by condensing for instance piperazine, alkylpiperazines, 1,4-bis-(3-aminopropyl)piperazine, imidazole, alkylimidazoles or their mixtures with a crosslinking agent selected from alkylene dihalides, epihalohydrins and/or bisepoxides. At least 25%, preferably at least 50% of the amino groups of the condensation products may be quaternized.
The cationic condensation products described above have color-fixing properties and more or less additionally fix soil from the wash liquor on the textile material during the wash. Moreover, many of the said cationic condensation products are not stable in detergents which contain a bleaching agent. It is therefore the object of the invention to provide new cationic polymers which are stable against bleaching agents containing detergents and which have a better wash performance.
We have found that this objective is achieved with a cyclic amine based polymer substantially free of primary and secondary amino groups wherein the said polymer is prepared by reacting
a) an amine selected from the group consisting of cyclic amines having at least one nitrogen atom in the ring and at least one primary aminoalkyl group attached to the nitrogen atom of the ring and PA0 mixtures of cyclic amines containing at least two reactive nitrogen atoms with at least one other amine containing 1 to 6 nitrogen atoms with PA0 b) at least one crosslinker selected from the group consisting of at least one compound containing two reactive groups and mixtures of at least one compound containing two reactive groups with at least one compound containing at least three reactive groups PA0 (c) an alkylating agent selected from the group consisting of epoxides, alkyl halides, arylalkyl halides, dimethyl sulfate, diethyl sulfate, mixtures of formic acid and an aldehyde, and mixtures of formic acid and a ketone, to convert more than 80% of the primary and secondary nitrogen groups into tertiary nitrogen groups. PA0 (a) a cyclic amine having at least two reactive nitrogen atoms with PA0 (b) a mixtures of crosslinkers of at least one compound containing two reactive groups with at least one compound containing at least three reactive groups PA0 (a) imidazole with PA0 (b) a mixture of epichlorohydin and the triglycidyl ether of trimethylolpropane or a mixture of epichlorohydrin and the triglycidyl ether of pentaerythritol. PA0 (a) a cyclic amine having at least two reactive nitrogen atoms in the molecule with PA0 (b) a mixture of crosslinkers of at least one compound containing two groups which react with a compound having a non-quaternary nitrogen atom and at least one compound containing at least three groups which react with a compound having a non-quaternary nitrogen atom PA0 (a) imidazole with PA0 (b) a mixture of 85 to 98 mol % of epichlorohydrin and 2 to 15 mol % of the triglycidyl ether of trimethylol propane or of the triglycidyl ether of pentaerythritol. PA0 (a) 1,4-bis(aminopropyl)piperazine or a mixture of imidazole with at least one compound selected from the group consisting of dimethylamino propylamine, hexamethylenediamine, ethylenediamine, 1,3-diaminopropane and N,N-bis(3-aminopropyl)-N-methylamine with PA0 (b) epichloroydrin in a molar ratio of from 2.0:1 to1:1 with formation of a water-soluble cyclic amine based polymer containing primary or secondary amino groups and PA0 (c) alkylating the said cyclic amine based polymer with ethylene oxide, propylene oxide and/or a mixture of formic acid and formaldehyde to convert more than 95% or the primary and secondary amino groups into tertiary nitrogen groups. PA0 (a) an amine selected from the group consisting of (i) cyclic amines having at least one nitrogen atom in the ring and at least one primary aminoalkyl group attached to the nitrogen atom of the ring and (ii) mixtures of cyclic amines containing at least two reactive nitrogen atoms with at least one other amine containing 1 to 6 nitrogen atoms with PA0 (b) at leant one crosslinker selected from the group consisting of at least one compound containing two reactive groups and mixtures of at least one compound containing two reactive groups with at least one compound containing at least three reactive groups PA0 (c) an alkylating agent selected from the group consisting of epoxides, alkyl halides, arylalkyl halides, dimethyl sulfate, diethyl sulfate, mixtures of formic acid and an aldehyde, and mixtures of formic acid and a ketone, to convert more than 80% of the primary and secondary nitrogen groups into tertiary nitrogen groups. PA0 (a) a cyclic amine havng at least two reactive nitrogen atoms with PA0 (b) a mixtures of crosslinkers of at least one compound containing two reactive groups with at least one compound containing at least three reactive groups PA0 (1) Waters Ultrahydrogel 500 PA0 (2) Waters Ultrahydrogel 250 PA0 (3) Waters Ultrahydrogel 250 PA0 (4) Waters Ultrahydrogel 120.
in a molar ratio of (a):(b) of from 2.5:1 to 1:1.5 with formation of cyclic amine based polymer containing primary or secondary amino groups and reacting the said cyclic amine based polymer with
The above objective is also achieved with a cyclic amine based polymer substantially free of primary and secondary amino groups, wherein the said polymer is obtainable by reacting
in a molar ratio of (a):(b) of from 2.5:1 to 1:1.5 with formation of water-soluble cyclic amine based polymer substantially free of primary and secondary amino groups. The preferred compounds of this embodiment of the invention are obtainable by reacting
Suitable compounds of group (a) that can be used alone or in mixture with other amines are cyclic amines having at least one nitrogen atom in the ring and at least one primary aminoalkyl group attached to the nitrogen atom of the ring. Such compounds are for example monoaminoalkylpiperazines, bis(aminoalkyl)piperazines, monoaminoalkylimidazoles, aminoalkylmorpholines, aminoalkylpiperidines and aminoalkylpyrrolidines. The monoaminoalkylpiperazines are for example 1-(2-aminoethyl)piperazine and 1-(3-aminopropyl)piperazine. Preferred monoaminoalkylimidazoles have 2 to 8 carbons atoms in the alkyl group. Examples of suitable compounds are 1-(2-aminoethyl)imidazole and 1-(3-aminopropyl)imidazole that. Suitable bis(aminoalkyl)piperazines are for example 1,4-bis (-2-aminoethyl)piperazine and 1,4-bis(3-aminopropyl)-piperazine. Preferred aminoalkylmorpholines are aminoethylmorpholine and 4-(3-aminopropyl)-morpholine. Other preferred compounds of this group are aminoethylpiperidine, aminopropylpiperidine and aminopropylpyrrolidine.
Cyclic amines with at least two reactive nitrogen atoms that are used in mixture with at least one other amine are for example imidazole, C-alkyl substituted imidazoles having 1 to 25 carbon atoms in the alkyl group such as 2-methylimidazole, 2-ethylimidazole, 2-propylimidazole, 2-isopropylimidazole and 2-isobutylimidazole, imidazoline, C-alkyl substituted imidazolines having 1 to 25 carbon atoms in the alkyl group and arylimidazolines such as 2-phenylimidazoline and 2-tolylimidazoline, piperazine, N-alkyl-piperazines having 1 to 25 carbon atoms in the alkyl group such as 1-ethylpiperazine, 1-(2-hydroxy-1-ethyl)piperazine, 1-(2-hydroxy-1-propyl)piperazine, 1-(2-hydroxy-1-butyl)piperazine, 1-(2-hydroxy-1-pentyl)pipe-azine, 1-(2,3-dihydroxy-1-propyl)piperazine, 1-(2-hydroxy-3-phenoxyethyl)piperazine, 1-(2-hydroxy-2-phenyl-1-ethyl)piperazine,
N,N'-dialkylpiperazines having 1 to 25 carbon atoms in the alkyl group for example 1,4-dimethylpiperazine, 1,4-diethylpiperazine, 1,4-dipropylpiperazine, 1,4-dibenzylpiperazine, 1,4-bis(2-hydroxy-1-ethyl)piperazine, 1,4-bis(2-hydroxy-1-propyl)piperazine, 1,4-bis(2-hydroxy-1-butyl)piperazine, 1,4-bis(2-hydroxy-1-pentyl)piperazine, and 1,4-bis(2-hydroxy-2-phenyl-1-ethyl)piperazine. Other cyclic amines with at least two reactive nitrogen atoms are benzimidazoles such as 2-hydroxybenzimidazole and 2-aminobenzimidazole. Melamine is another example of a compound of group (a).
Preferred cyclic amines with at least two reactive nitrogen atoms are imidazole, 2-methylimidazole, 4-methylimidazole and piperazine.
The cyclic amines with at least two reactive nitrogen atoms are used in mixture with at least one other amine containing 1 to 6 nitrogen atoms of which at least one is not quaternary. Examples of such amines are linear alkyl amines having 1 to 22 carbon atoms in the alkyl group, branched alkylamines, cycloalkylamines, alkoxyamines, amino alcohols, cyclic amines containing one nitrogen atom in a ring structure, alkylenediamines, polyether diamines, and polyalkylenepolyamines containing 3 to 6 nitrogen atoms.
Specific examples of the said amines are methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, heptylamine, octylamine, 2-ethylhexylamine, isooctylamine, nonylamine, isononylamine, decylamine, undecylamine, dodecylaminetridecylamine, stearylamine, palmitylamine,
dimethylamine, diethylamine, dipropylamine, dibutylamine, dipentylamine, dihexylamine, bis-(2-ethyl-hexyl)amine, ditridecylamine, N-methylbutylamine, N-ethylbutylamine, piperidine, morpholine, pyrrolidine,
2-methoxyethylamine, 2-ethoxyethylamine, 3-methoxypropylamine, 3-ethoxypropylamine, 3-[(2-ethylhexyl)oxy]-1-propaneamine, 3-[(2-methoxyethoxy]-1-propaneamine, 2-methoxy-N-(2-methoxyethyl)ethanamine,
2-aminoethanol, 3-amino-1-propanol, 1-amino-2-propanol, 2-(2-aminoethoxy)ethanol, 2-[(2-aminoethyl)amino]ethanol, 2-(methylamino)ethanol, 2-(ethylamino)ethenol, 2-(butylamino)ethanol, diethanolamine, 3-[(2-hydroxyethyl)amino] 1-propanol, diisopropanolamine, bis-(2-hydroxyethyl)aminoethylamine, bis-(2-hydroxypropyl)aminoethylamine, bis-(2-hydroxyethyl)aminopropylamine, bis-(2-hydroxypropyl)aminopropylamine,
cyclopentylamine, cyclohexylamine, N-methylcyclohexylamine, N-ethylcyclohexylamine, dicyclohexylamine, ethylenediamine, propylenediamine, butylenediamine, neopentyldiamine, hexamethylenediamine, octamethylenediamine, isophoronediamine, 4,4,-methylene-biscyclohexylamine, 4,4'-methylenebis(2-methylcyclohexylami ne), 4,7-dioxadecyl-1,10-diamine, 4,9-dioxadodecyl-1,12-diamine, 4,7,10-trioxatridecyl-1,13-diamine, 2-(ethylamino)ethylamine, 3-(methylamino)propylamine, 3-(cyclohexylamino)propylamine, 3-aminopropylamine, 2-(diethylamino)ethylamine, 3-(dimethylamino)propylamine, 3-(diethylamino)propylamine, dipropylenetriamine, tripropylenetetramine, N,N-bis-(aminopropyl)methylamine, N,N-bis-(aminopropyl)ethylamine, N,N-bis-(aminopropyl)hexylamine, N,N-bis-(aminopropyl)octylamine, 1,1-dimethyldipropylenetriamine, N,N-bis-(3-dimethylaminopropyl)amine, N,N"--1,2-ethanediyl-bis-(1,3-propanediamine), diethylenetriamine, bis-(aminoethyl)ethylenediamine, bis-(aminopropyl)ethylenediamine, bis-(hexamethylene)triamine, N-(aminoethyl)hexamethylenediamine, N-(aminopropyl)hexamethylenediamine, N-(aminopropyl) ethylenediamine, N-(aminoethyl)butylenediamine, N-(aminopropyl)butylenediamine, bis-(aminoethyl)hexamethylenediamine, bis-(aminopropyl)hexamethylenediamine, bis-(aminoethyl)butylenediamine, bis-aminopropyl)butylenediamine, 4-aminomethyloctane-1,8-diamine, and N,N-diethyl-1,4-pentanediamine.
Preferred amines that are used in mixture with at least one cyclic amine with at least two reactive nitrogen atoms are methylamine, ethylamine, propylamine, ethylenediamine, 1,4-diaminobutane, 1,2-diaminobutene, 1,3-diaminopropane, 1,2-diaminopropane, hexamethylenediamine, bishexamethylenetriamine, diethylenetriamine, dipropylenetriamine, triethylentetramine, tetraethylenepentamine, dimethylaminopropylamine and N,N-bis(3-aminopropyl)-N-methylamine.
Most preferred amines that are used in mixture with at least one cyclic amine with at least two reactive nitrogen atoms are ethylenediamine, 1,3-diaminopropane, hexamethylenediamine, dimethylaminopropylamine and N,N-bis(3-aminopropyl)-N-methylamine.
The term "reactive nitrogen atom" means that this nitrogen atom is capable of reacting with for example an alkylating agent, e.g. benzyl chloride, or with a crosslinker, e.g. ethylene chloride or epichlorohydrin and excludes quaternary nitrogen atoms which cannot react further. In accordance with the said meaning primary, secondary and tertiary amino groups contain one reactive nitrogen atom, whereas imidazole contains two.
The amines of group (a) are reacted with at least one crosslinker. The crosslinker based on compounds containing two reactive groups is selected from the group consisting of alkylene dihalides, epihalohydrins, bis(halohydrins) of diols, bis(halohydrins) of polytetrahydrofuran, bisepoxides. Examples of alkylene dihalides which may have 2 to 6 carbon atoms in the alkylene group are 1,2-dichloroethane, 1,2-dichloropropane, 1,3-dichloropropane, 1,4-dichlorobutane, 1,6-dichlorohexane, 1,3-dichloropropane-2ol, 1,2-dichloropropane-3-ol. Epihalohydrins are epichlorohydrin, epibromohydrin and epi-iodohydrin. Bis(halohydrins) of diols are for example derived from alkylene glycols and polyalkylene glycols, e.g. bis(chlorohydrins) of ethylene glycol, polyethylene glycol containing 2 to 100 ethylene oxide units, propylene glycol, polypropylene glycol containing 2 to 70 propylene oxide units, 1,2-butanediol, 1,4-butanediol, 1,2-pentanediol, 1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol, 2,2-dimethyl-1,3-propanediol, bis(hydroxyphenyl)methane, 2,2-bis(hydroxyphenyl)propane and polytetrahydrofurans having 2 to 50 tetrahydrofuran units.
The bis(halohydrins) can be converted into bisepoxides via dehydrohalogenation by treatment with a base such as sodium hydroxide or potassium hydroxide. Another suitable bisepoxide is bisepoxybutane.
Crosslinkers which contain at least three reactive groups are for example C3- to C10-alkylene trihalides, reaction products of polyols having at least three hydroxy groups with epihalohydrins in a molar ratio of at least 1:3 or their dehydrohalogenation products. Polyols with at least three hydroxy groups are for example glycerol, pentaerythritol, sorbitol, and trimethylolpropane. Dehydrohalogenation products are e.g. poly-[(phenyl-2,3-epoxypropylether)-co-formaldehyde (=epoxi-phenol-novolak with CAS-No. 39362-23-7 und 28064-14-4), poly-{2,2-[4,4'-bis-(2,3-epoxyprpopyloxyphenyl)propane]}-co-formaldehyde (=epoxi-bis-A-novolak), bis-{4-[bis-(2,3-epoxypropyl)amino]phenyl}methane (with CAS-No. 28768-32-3), and 1,3,5-tris-(2,3-epoxypropyl)1,3,5-triazin-1H,3H,5H,2,4,6-trion (=isocyanuric acid-(2,3-epoxypropyl)-ester, CAS-No. 2451-62-9). The molecular weight of the crosslinkers usually does not exceed 3000 and is preferably in the range of from 92 to 2000.
Preferred cyclic amine based polymers contain in condensed form as crosslinker with at least three reactive groups C3- to C10-alkylene trihalides or reaction products of polyols having three to six hydroxy groups with epihalohydrins in a molar ratio of at least 1:3. The most preferred crosslinkers are epichlorohydrin, the triglycidyl ether of trimethylolpropane, the triglycidyl ether of pentaerythritol, and mixtures thereof.
The compounds of groups (a) and (b) are reacted in a molar ratio ot (a):(b) of from 2.5:1 to 1:1.5 with the formation of cyclic mine based polymers which contain primary and secondary amino groups. The reaction is preferably carried out in a solvent at temperatures of from 20 to 120.degree. C. If the reaction temperature is above the boiling point of the solvent, then the reaction is carried out in a pressure-tight apparatus under elevated pressure. Suitable solvents are alcohols, e.g. methanol, ethanol, n-propanol, isopropanol and butanols, ethers such as dimethyl glycols or tetrahydrofuran, and water, which is the preferred solvent.
The reaction of the primary and secondary amino groups containing cyclic amine based polymers with the alkylating agents (c) is preferably carried out in a solvent at temperatures from 20-180.degree. C. In case of gaseous alkylating agents like e.g. ethylene oxide and propylene oxide the reaction is carried out in an autoclave under elevated pressure. The pressure applied can be varied in a broad range and is typically in the range of from 1-50 bar, preferably 1.5-20 bar. Suitable solvents are alcohols, e.g. methanol, ethanol, n-propanol, isopropanol and butanols, ethers such as dimethyl glycols or tetrahydrofuran, and water, which is the preferred solvent.
In order to convert the primary and secondary amino groups of the cyclic amine based polymers to tertiary amino groups without quaternization the amount of alkylating agent (c) is preferably less then 1,1 times, most preferred less then 1,0 times the molar amount of the N--H bonds in the polymer if a alkylating agent is used, that is capable of alkylating tertiary amines under the applied conditions.
One mole of a crosslinker with two reactive groups (e.g. epichlorohydrin) corresponds to two moles of epoxide equivalents and one mole of crosslinker with -three reactive groups (e.g. trimethylolpropane triglycidyl ether) corresponds to three moles of epoxide equivalents. The mixture of crosslinkers which contain at least one crosslinker with two reactive groups (e.g. two epoxide groups) and at least one crosslinker with at least three reactive groups (e.g. at least three epoxide groups) contains 1 to 30, preferably 2 to 20 and most preferred 5 to 10 mol % of the crosslinker with at least three reactive groups.
Preferred cyclic amine based polymers are obtained by reacting
directly form water-soluble cyclic amine based polymers which are substantially free or primary and secondary amino groups.
Most preferred are polymers which are obtained by reacting
Condensation products of the compounds of groups (a) and (b) which still contain primary and/or secondary amino groups are further reacted with (c) an alkylating agent selected from the group consisting of epoxides, alkyl halides, arylalkyl halides, dimethyl sulfate, diethyl sulfate, mixtures of formic acid and an aldehyde, and mixtures of formic acid and a ketone, to convert more than 80% of the primary and secondary nitrogen groups into tertiary nitrogen groups. In a preferred embodiment of the invention more than 90% of the primary and secondary nitrogen groups of the condensation product of (a) and (b) are converted into tertiary nitrogen groups by reacting them with (c) an alkylating agent selected from the group consisting of ethylene oxide, propylene oxide, C1- to C3- alkyl halide, dimethyl sulfate, diethyl sulfate, and a mixture of formic acid and a C1- to C3- aldehyde. Cyclic amine based polymers wherein more than 90% of the primary and secondary nitrogen groups of the condensation product of (a) and (b) are converted into tertiary nitrogen groups by reacting them with (c) ethyleneoxide, propyleneoxide and/or a mixture of formic acid and formaldehyde are most preferred. Such products are for example obtained by reacting
The cyclic amine based polymers which are substantially free of primary and secondary amino groups are produced by reacting
in a molar ratio of (a):(b) of from 2.5:1 to 1:1.5 with formation of a cyclic amine based polymer containing primary or secondary amino groups and reacting the said cyclic amine based polymer with
Cyclic amine based polymer substantially free of primary and secondary amino groups are also produced by reacting
in a molar ratio of (a):(b) of from 2.5:1 to 1:1.5. Water-soluble cyclic amine based polymers which are substantianlly free of primary and secondary amino groups are obtained.
Suitable amines of component (a), crosslinkers (b) and alkylating agents (c) are specified above. According to a preferred embodiment of the invention more than 90% of the primary and secondary nitrogen groups of the condensation product of (a) and (b) are converted into tertiary nitrogen groups by reacting them with (c) an alkylating agent selected from the group consisting of ethylene oxide, propylene oxide, C1- to C3- alkyl halide, dimethyl sulfate, diethyl sulfate, and a mixture of formic acid and a C1- to C3- aldehyde.
According to a preferred embodiment of the invention (a) 1,4-bis(aminopropyl)piperazine or a mixture of imidazole with at least one compound selected from the group consisting of dimethylamino propylamine, hexamethylenediamine and ethylendiamine, 1,3-diaminopropane, N,N-bis(3-aminopropyl)-N-methylamine are reacted first with (b) epichlorohydrin in a molar ratio of from 2.0:1 to 1:1 with formation of a water-soluble cyclic amine based polymer containing primary or secondary amino groups and then with (c) ethylene oxide, propylene oxide and/or a mixture of formic acid and formaldehyde to convert more than 95% of the primary and secondary amino groups into tertiary nitrogen groups. Another preferred embodiment of the invention is a single-stage process wherein (a) imidazole is reacted with a mixture of (b) epichlorohydrin and the triglycidyl ether of trimethylol of with a mixture of epichlorohydrin and the triglycidyl ether of pentaerythritol.
The process of the invention gives cyclic amine based polymers which are substantially free of aliphatic primary, secondary and quaternary amino or ammonium groups. The content of quaternary ammonium groups in the said polymers obtained by alkylation with component (c) does not exceed 20 mol % and is usually below 10 mol %. Cyclic amine based polymers free of aliphatic quaternary ammonium groups are most preferred. The content of primary, secondary and tertiary amino groups and quaternary amonium groups in the polymers can be determined by several methods, e.g. 13C-NMR spectroscopy, :1H-NMR spectroscopy, infrared spectroscopy, polyelectrolyte titration and potentiometric titration.
The cyclic amine based polymers which are substantially free of primary and secondary amino groups and preferably free of aliphatic quaternary ammonium groups can be used as additives in detergents in an amount of from 0.1 to 5% by weight. Laundering treating of fabrics and textiles in aqueous washing or treating solutions which contain an effective amount of the cyclic amine based polymer of the invention, followed by rinsing and drying, imparts fabric appearance benefits to the fabric and textile articles so treated. Such benefits can include improved overall appearance, pill/fuzz reduction, antifading, improved abrasion resistance, and/or enhanced softness.
The percentages in the Examples are by weight. The K values were determined according to Fikentscher, Cellulose-Chemie Vol. 13, 58-64 and 71-74 (1932) in 5% strength aqueous solution of sodium chloride, a polymer concentration of 1% by weight and at a temperature of 25.degree. C.
The molecular weights were measured by gel permeation chromatography (GPC) using the following combination of separating columns:
The temperature of the columns was 35.degree. C. The eluant consisted of a mixture of a 0.2 molar acetic acid and a 0.3 molar aqueous potassium chloride solution, the flow rate was 0.5 ml/min. The calibration was carried out with narrowly distributed standards of pullulan obtained from Polymer Laboratories LTD with molecular weights M=5,800 to 853,000 and maltohexose (M=992), saccharose (M=342) and glucose (M=180). Differental refractometer ERC 7510 (ERMA) was used as detector.